Rhodium-catalyzed multicomponent-coupling reactions involving a carborhodation-cross-coupling sequence

[reaction: see text] A rhodium-catalyzed multicomponent-coupling reaction has been developed that involves a cross-coupling with organohalides as part of the reaction sequence. Through several experiments toward mechanistic investigations, it has also been demonstrated that the reaction most likely proceeds via a carborhodation-oxidative addition-reductive elimination pathway, which clearly contrasts to the corresponding palladium-catalyzed processes.     

Synthesis of Cp*CH2PPh2 and its use as a ligand for the nickel-catalysed cross-coupling reaction of alkyl halides with aryl Grignard reagents

A new ligand, Cp*CH2PPh2 (Cp* = 1,2,3,4,5-pentamethyl-2,4-cyclopentadienyl), was prepared, and was used as a ligand for nickel-catalysed cross-coupling reaction of alkyl halides with aryl Grignard reagents, which nickel-phosphine complexes had never made possible.     

Lyngbyacyclamides A and B, novel cytotoxic peptides from marine cyanobacteria Lyngbya sp.

Lyngbyacyclamides A (1) and B (2), novel cyclic peptides, were isolated from marine cyanobacteria Lyngbya sp. collected in Okinawa, Japan. Their structures were determined by spectroscopic analyses and degradation studies. They moderately inhibited the growth of B16 mouse melanoma cells.     

A short synthesis of 3-oxa- and 3-azabicyclo[3.1.0]hexanes from α,β-unsaturated esters based on the 1,5-CH insertion reaction of cyclopropylmagnesium carbenoids

1-Chlorocyclopropyl p-tolyl sulfoxides bearing an alkoxymethyl group at the 2-position were easily prepared from α,β-unsaturated esters with dichloromethyl p-tolyl sulfoxide and alkylhalides in three steps in good overall yields. Treatment of the 1-chlorocyclopropyl p-tolyl sulfoxides with i-PrMgCl resulted in the formation of 3-oxabicyclo[3.1.0]hexanes in up to 89% yield as a single diastereomer via the 1,5-CH insertion reaction of the generated cyclopropylmagnesium carbenoid intermediates. This procedure provides a good way for the synthesis of 3-oxabicyclo[3.1.0]hexanes from α,β-unsaturated esters in only four steps. 3-Aza- and 3-thiabicyclo[3.1.0]hexanes were also obtained from the corresponding precursors via the 1,5-CH insertion reaction of the cyclopropylmagnesium carbenoid intermediates, though the yields were low to moderate.     

Liquid structures of 1-butyl-3-methylimidazolium tetrafluoroborate and carbon dioxide mixtures by X-ray diffraction measurements

X-ray diffraction measurements for the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF₄], mixed with CO₂ were carried out at high pressures using our developed polymer cell. The intermolecular distribution functions obtained for [BMIM][BF₄]–CO₂ mixtures showed that CO₂ molecules are preferentially solvated to the [BF₄]⁻ anion. The similar preferential solvation was previously observed in analogous 1-btuyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF₆], with a different anion, which is in harmony with the present results in [BMIM][BF₄]–CO₂.     

Investigation of nonpolar (1 1 2¯ 0) a-plane ZnO films grown under various Zn/O ratios by plasma-assisted molecular beam epitaxy

Structural and optical properties of nonpolar a-plane ZnO films grown with different II/VI ratios on r-plane sapphire substrates by plasma-assisted molecular beam epitaxy were investigated. Even by increasing the II/VI ratio across the stoichiometric flux condition a consistent surface morphology of striated stripes along the ZnO 〈0 0 0 1〉 direction without any pit formation was observed, which is contrary to polar c-plane ZnO films. Root mean square surface roughness, full width at half maximum values of X-ray rocking curves, defect densities, and photoluminescence were changed with the II/VI ratio. The sample grown with stoichiometric flux condition showed the lowest value of rms roughness, the smallest threading dislocation and stacking fault densities of ∼4.7×10⁸ cm⁻² and ∼9.5×10⁴ cm⁻¹, respectively, and the highest intensity of D^oX peak. These results imply that the stoichiometric flux growth condition is suitable to obtain superior structural and optical properties compared to other flux conditions.